US3835119A - Poly (phosphine oxide derivative) with ammonium polyphosphate as a flame retardant composition for polymers - Google Patents
Poly (phosphine oxide derivative) with ammonium polyphosphate as a flame retardant composition for polymers Download PDFInfo
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- US3835119A US3835119A US00374728A US37472873A US3835119A US 3835119 A US3835119 A US 3835119A US 00374728 A US00374728 A US 00374728A US 37472873 A US37472873 A US 37472873A US 3835119 A US3835119 A US 3835119A
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- benzene
- flame
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- methyl
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- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 229920000642 polymer Polymers 0.000 title claims abstract description 35
- 229920001276 ammonium polyphosphate Polymers 0.000 title abstract description 22
- 239000004114 Ammonium polyphosphate Substances 0.000 title abstract description 19
- 239000003063 flame retardant Substances 0.000 title abstract description 18
- 235000019826 ammonium polyphosphate Nutrition 0.000 title abstract description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 16
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical class P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 title abstract description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 54
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 27
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 25
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 17
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract description 4
- 125000005577 anthracene group Chemical group 0.000 abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 229920001169 thermoplastic Polymers 0.000 description 9
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000011885 synergistic combination Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- KZNJSFHJUQDYHE-UHFFFAOYSA-N 1-methylanthracene Chemical compound C1=CC=C2C=C3C(C)=CC=CC3=CC2=C1 KZNJSFHJUQDYHE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- KDGJZSSWFPNTJU-UHFFFAOYSA-N O=[PH3].N Chemical compound O=[PH3].N KDGJZSSWFPNTJU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910004856 P—O—P Inorganic materials 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DSIQDXZNQNRKSD-UHFFFAOYSA-N bis(2-cyanoethyl)-oxophosphanium Chemical compound N#CCC[P+](=O)CCC#N DSIQDXZNQNRKSD-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- UOHMMEJUHBCKEE-UHFFFAOYSA-N tetramethylbenzene Natural products CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5304—Acyclic saturated phosphine oxides or thioxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5333—Arylalkane phosphine oxides or thioxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Definitions
- ABSTRACT Flame-retardant compositions comprising (a) a poly (phosphine oxide derivative) having the formula wherein R and R are individually, methyl, ethyl or methoxy radicals, AR is benzene, napthalene or anthracene and when AR is benzene, n and m are individually whole integers of 0-2, inclusive, x is a whole integer of 2-6, inclusive and R and R can combine to form a saturated, six-membered hydrocarbon ring in conjunction with two adjacent carbon atoms of the benzene ring, when AR is napthalene, n and m are individually, whole integers of 0-3, inclusive, and x is a whole integer of 2-4, and when AR is anthracene, n and m are, individually, whole integers of 0-4, inclusive, and x is a poly (phosphine oxide derivative) having the formula wherein R and R are individually, methyl, ethyl or methoxy radicals, AR is
- thermoplastic polymers such as, for example, polypropylene.
- these combinations although effective flame retardants for thermoplastics have been found to be relatively incompatible with many polymers such as, for example, polypropylene.
- polymers such as, for example, polypropylene.
- they are extremely difficult to incorporate into such polymers, especially with regard to the phosphine oxide component thereof, by conventional extrusion and injection molding techniques since they tend to exude from the polymer. Therefore, uniform dispersions of the alkylenebisphosphine oxide-ammonium polyphosphate combinations are difficult to achieve.
- a second, and sometimes more detrimental, disadvantage of these known flameretardant combinations resides in the fact that the phosphine oxide components thereof are relatively water-soluble and in certain applications of the polymers to which they are added, such as components in dish and clothes washers, they tend to be extracted out of the polymer upon contact thereof with water. Consequently the polymer becomes more readily flammable and ultimately fails to pass the Underwriters Laboratory test of acceptable flame-retardance.
- thermoplastic polymers a combination of ammonium polyphosphate and a compound conforming to the formula set forth hereinabove.
- novel combinations impart flameretardance to thermoplastic polymers at relatively low concentrations, are easily incorporated into the polymers using conventional techniques and do not leach out of the polymer when it is used in conjunction with water after having been formed into a particular article of manufacture.
- thermoplastic polymers by incorporating into the polymer a synergistic combination of ammonium polyphosphate and a compound conforming to at least one of the following formulae (III) R!
- R R R R R and R are, individually, methyl ethyl or methoxy radicals, and R and R can combine to form a saturated, six-membered, hydrocarbon ring in conjunction with two adjacent carbon atoms of the benzene ring; a and b are, individually, whole integers of 0-2, inclusive; c and d are, individually, whole integers of 03, inclusive; e and f are, individually, whole integers of 04, inclusive; w is a whole integer of 2-6, inclusive; y is a whole integer of 2-4, inclusive, and z is a whole integer of 2-6, inclusive.
- Among the preferred compounds are those represented by Formula I, including 5,8-bis[bis(2- cyanoethyl)phosphonyl-methylene]tetralin; l ,4- bis[bis(2-cyanoethyl)phosphonylmethylene]-2,3,5,6- tetramethyl benzene; l ,2,4,5-tetrakis[ bis-( 2- cyanoethyl)phosphonylmethylene]benzene; 2,4,6- tris[bis(Z-cyanoethyl)phosphonylmethylenelmesitylene; and l,4-phenylene-bis[bis(2-cyanoethyl)phosphonylmethylene; 2,4-bis[bis(2- cyanoethyl)phosphonylmethylene l ,3 ,S-trimethyl benzene and the like.
- Formula I including 5,8-bis[bis(2- cyanoethyl)phosphonyl-methylene]tetralin; l
- Compounds falling within the scope of Formulae II and III include l,5-bis[bis(2-cyanoethyl)phosphonylmethylene lnaphthalene; 9, l 0-bis[ bis( 2-cyanoethyl phosphonylmethylene]anthracene; 2,6-bis[bis(2- cyanoethyl)phosphonylmethylene]naphthalene; 2,3,6- tris[bis(2-cyanoethyl)phosphonylmethylene]naphthalene; 2,3,6-tris[bis(2- cyanoethyl)phosphonylmethylene]anthracene; 2,6,9,- l0-tetra[bis(2-cyanoethyl)phosphonylmethylene]anthracene; 1,6-bis[bis(2- cyanoethyl)phosphonylmethylene]-2-methoxy naphthalene; 2,3-bis[bis(2- cyanoethyl)phosphony
- poly (phosphine oxide) compounds used in forming the novel flame-retardant combinations of the instant invention are readily prepared by reacting bis(2-cyanoethyl)phosphine oxide with the appropriately substituted aromatic compound, in accordance with the general reaction:
- X is a halogen and x, n, m, R, R and AR are as set forth above.
- the intermediate halomethylated aromatic compounds may conveniently be prepared by reacting the corresponding benzene, naphthalene or anthracene ages.
- the poly (phosphine oxides) may be prepared according to the above general reaction in an organic solvent which is inert to the reaction and the components thereof. Methanol has been found to be an effective solvent, however, other alcohols may also be used.
- the reaction is best conducted in the presence of a proton acceptor such as a strong base e. g. potassium or sodium hydroxide, in amounts equivalent to the amount of hydrogen halide evolved.
- a proton acceptor such as a strong base e. g. potassium or sodium hydroxide
- the reaction is generally conducted at a temperature ranging from about 10C. to about 60C. under atmospheric pressure. Subatmospheric or superatmospheric pressure can be used, if desired. No catalysts are necessary.
- ammonium polyphosphates which constitute the second critical component of my novel flame-retardant compositions are well known in the art as shown in U.S. Pat. Nos. 3,423,343 and 3,513,114, which patents are hereby incorporated herein by reference.
- These ammonium polyphosphates are generally substantially waterinsoluble and possess a plurality of P-O-P type link- They can be represented by formula wherein g is an integer having an average value greater than 10, h/g is between about 0.7 and about 1.1 and the maximum value of h is equal to g+2. They are straight or branched chain structures having nearly all the nitrogen present therein as ammonical nitrogen.
- the average numerical value of g, using end group titration after acid formation, is from about 20-400, while using the light scattering method, the average weight value of n is above about 500, preferably 500l00,000 and especially preferably LOGO-30,000.
- the ammonium polyphosphates exhibit different crystalline forms but are also found in the non-crystalline or amorphous form also.
- the combination of poly (phosphine oxide) and ammonium polyphosphate may be incorporated into the thermoplastic polymers in flame-retarding amounts. Concentrations of from about l25 percent, by weight, preferably from about 15-25 percent, by weight, based on the weight of the polymer, of the combination have been found effective. The ratio of poly (phosphine oxide) to ammonium polyphosphate should range from about 2:1 to about 1:2, respectively.
- compositions of my invention may be incorporated into the polymers by any known method.
- the composition may be combined with the polymer by milling the two on a two-roll mill, mixing in a Banbury mixer, extrusion, injection molding or the like.
- the combination may also be incorporated into the polymer by adding it to the polymerization media during the polymer manufacture, provided the ingredients, catalysts etc. therein are inert thereto.
- thermoplastic polymers to which the novel poly (phosphine oxide)-ammonium polyphosphate compositions may be incorporated to produce the novel flame-retarded compositions of the instant invention are generally those produced from at least one ethylenically unsaturated monomer, wherein the monomer, or monomers, are polymerized, by any known method, via the ethylenic unsaturation therein.
- Preferred examples of polymers conforming to this definition include the polyolefins i.e., those polymers produced from ethylene, propylene etc. including copolymers thereof with such monomers as vinyl acetate etc. and homopolymers thereof i.e., polyethylene; polypropylene etc.
- I may also use the linear aromatic polyesters such as polyethylene terephthalate; polybutylene terephthalate; poly (l,4-cyclohexanedimethylene )terephthalate etc.; the polyalkylene oxides such as polyethylene oxide; nylon; rayon; polyphenylene oxide; butadiene polymers such as the so-called impact polymers i.e., acrylonitrilebutadiene-styrene polymers; acrylonitrilestyrene-methyl methacrylate grafted polybutadiene; cellulose acetate and propionate; etc.
- impact polymers i.e., acrylonitrilebutadiene-styrene polymers; acrylonitrilestyrene-methyl methacrylate grafted polybutadiene; cellulose acetate and propionate; etc.
- Further examples of polymers which may be flameproofed are set forth in US. Pat. No. 3,284,543, hereby incorporated herein by
- EXAMPLE 1 Ten parts of l,4-bis[bis(2-cyanoethyl)phosphonyl methylene]2,3,5,6-tetramethyl benzene and 15 parts of ammonium polyphosphate are dry blended with polypropylene, extruded at 420F. and chopped into pellets. The pellets are then injection molded at 400-450F. in bars /4 inch X Va inch X 5 inches. Sample bars are then measured for flammability in accordance with Underwriters Laboratory Test UL-94 be fore and after subjection to UL Water Extraction Test, Subject 746, Mar. 1, 1957, paragraph E6. The water extraction test requires that the samples be immersed in water at C. for 7 days, the water being changed daily for the first five days. At the end of the immersion, the bars are dried in a dessicator before burning. Before and after extraction, each bar is designated as self-extinguishing.
- the metal oxides or carbonates are added to the polymer in an amount ranging from about 0.5 percent to about 5 percent, by weight, based on the weight of the polymer.
- the manner in which the metal oxide or carbonate is added is not critical and it can be added to the polymer before, along with or after the phosphine oxide-ammonium polyphosphate combination. Arnourrtshigher than about 5 percent are generally undesirable. l have found that alkaline earth metal oxides such as barium oxide, magnesium oxide, etc.; alkaline earth metal carbonates such as magnesium carbonate, calcium carbonate etc.; Group IV-A metal oxides such as silicon dioxide, stannic oxide, etc.; titanium dioxide; zinc oxide; antimony oxide and the like can be used.
- Example 21 The procedure of Example 21 is again conducted except that a ratio of poly (phosphine oxide) to ammonium polyphosphate to titanium dioxide is 10/10/1 is used. The resultant composition is again rated as selfextinguishing.
- Example 30 The procedure of Example 1 is again followed except that 2,5-bis[bis(2-cyanoethyl)phosphonylmethylene]- 1,4-dimethylbenzene is used at a ratio of poly (phosphine oxide) to ammonium polyphosphate to titanium dioxide of 10/ 10/ 1 is used and the polymer to which it is added is polypropylene. The resultant composition is again rated self-extinguishing.
- a flame-retardant composition comprising (a) a compound having the formula wherein R and R are, individually, methyl, ethyl or methoxy radicals, AR is benzene, naphthalene, or anthracene and when AR is benzene, n and m are, individually, whole integers of 0-2, inclusive, x is a whole integer of 2-6, inclusive, and R and R can combine to form a saturated, six-membered, hydrocarbon ring in conjunction with two adjacent carbon atoms of the benzene ring, when AR is naphthalene, n and m are, individually, whole integers of O3, inclusive, and x is a whole integer of 2-4, inclusive, and when AR is anthracene, n and m are, individually, whole integers of 0-4, inclusive, and x is a whole integer of 2-6, inclusive, and (b) ammonium polyphosphate.
- a composition according to claim 1 containing, in addition thereto, (c) from about 0.5 percent to about 5.0 percent, by weight, based on the weight of the polymer to which the composition is to be added of (1) an alkaline earth metal carbonate, (2) an alkaline earth metal oxide, (3) a Group IV-A metal oxide, (4) titanium dioxide, (5) zinc oxide or (6) antimony oxide.
- composition according to claim 9 wherein (a) is present at about 10 percent, (b) is present at about 10 percent and (c) is present at about 1.0 percent.
- a flame-retarded polymer comprising a polyolefin or a linear aromatic polyester and a flame-retarding amount of a composition of claim 1.
- a flame-retarded composition comprising a polyolefin or a linear aromatic polyester and a flameretarding amount of a composition of claim 6.
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Abstract
WHEREIN R and R1 are individually, methyl, ethyl or methoxy radicals, AR is benzene, napthalene or anthracene and when AR is benzene, n and m are individually whole integers of O-2, inclusive, x is a whole integer of 2-6, inclusive and R and R1 can combine to form a saturated, six-membered hydrocarbon ring in conjunction with two adjacent carbon atoms of the benzene ring, when AR is napthalene, n and m are individually, whole integers of 0-3, inclusive, and x is a whole integer of 2-4, and when AR is anthracene, n and m are, individually, whole integers of 0-4, inclusive, and x is a whole integer of 2-6, inclusive, and (b) ammonium polyphosphate and flame-retardant polymers containing the same, are disclosed.
Flame-retardant compositions comprising (a) a poly (phosphine oxide derivative) having the formula
Flame-retardant compositions comprising (a) a poly (phosphine oxide derivative) having the formula
Description
United States Patent [191 Hoffman Sept. 10, 1974 [75] Inventor: Joseph Adrian Hoffman, Somerville,
[73] Assignee: American Cyanamid Company,
Stamford, Conn.
[22] Filed: June 28, 1973 [21] Appl. No.: 374,728
[52] US. Ci..... 260/45.75 R, 252/8.l, 260/45.75 K, 260/465 F, 260/465 H [51] Int. Cl..... C08g 45/56, C08g 51/60, C09k 3/28 [58] Field of Search..... 260/45.9 NP, 465 F, 465 H, 260/45.75 R, 45.75 K; 252/8.1
[56] References Cited UNITED STATES PATENTS 2,666,078 l/l954 Ferguson 252/8.l 3,663,502 5/1972 Murry et al 252/8.1 3,783,l46 i/l974 Savides et al 260/45.9 NP
Primary Examiner-Donald E. Czaja Assistant ExaminerGary R. Marshall Attorney, Agent, or Firm-Frank M. Van Riet [57] ABSTRACT Flame-retardant compositions comprising (a) a poly (phosphine oxide derivative) having the formula wherein R and R are individually, methyl, ethyl or methoxy radicals, AR is benzene, napthalene or anthracene and when AR is benzene, n and m are individually whole integers of 0-2, inclusive, x is a whole integer of 2-6, inclusive and R and R can combine to form a saturated, six-membered hydrocarbon ring in conjunction with two adjacent carbon atoms of the benzene ring, when AR is napthalene, n and m are individually, whole integers of 0-3, inclusive, and x is a whole integer of 2-4, and when AR is anthracene, n and m are, individually, whole integers of 0-4, inclusive, and x is a whole integer of 2-6, inclusive, and (b) ammonium polyphosphate and flame-retardant polymers containing the same, are disclosed.
16 Claims, No Drawings POLY (PHOSPHINE OXIDE DERIVATIVE) WITH AMMONIUM POLYPI-IOSPHATE AS A FLAME RETARDANT COMPOSITION FOR POLYMERS CROSS-REFERENCE TO RELATED APPLICATION 5 This application is related to my copending application, Ser. No. 374,709, filed of even date herewith and entitled POLY (PHOSPI-IINE OXIDE) FLAME- RETARDANTS.
BACKGROUND OF THE INVENTION The use of combinations of ammonium polyphosphate and alkylenebisphosphine oxides to flame-proof 15 thermoplastic polymers is known, see US. Pat. No. 3,663,502. These combinations, although effective flame retardants for thermoplastics have been found to be relatively incompatible with many polymers such as, for example, polypropylene. As a result, they are extremely difficult to incorporate into such polymers, especially with regard to the phosphine oxide component thereof, by conventional extrusion and injection molding techniques since they tend to exude from the polymer. Therefore, uniform dispersions of the alkylenebisphosphine oxide-ammonium polyphosphate combinations are difficult to achieve. A second, and sometimes more detrimental, disadvantage of these known flameretardant combinations resides in the fact that the phosphine oxide components thereof are relatively water-soluble and in certain applications of the polymers to which they are added, such as components in dish and clothes washers, they tend to be extracted out of the polymer upon contact thereof with water. Consequently the polymer becomes more readily flammable and ultimately fails to pass the Underwriters Laboratory test of acceptable flame-retardance.
SUMMARY 1 have now discovered that these and other less objectionable deficiencies of the alkylenebisphosphine oxideammonium polyphosphate combinations can be overcome, and excellent flame-retardant properties can be achieved, by incorporating into thermoplastic polymers a combination of ammonium polyphosphate and a compound conforming to the formula set forth hereinabove. These novel combinations impart flameretardance to thermoplastic polymers at relatively low concentrations, are easily incorporated into the polymers using conventional techniques and do not leach out of the polymer when it is used in conjunction with water after having been formed into a particular article of manufacture.
DESCRIPTION OF THE INVENTION INCLUDING PREFERRED EMBODIMENTS As mentioned briefly above, I have now found that excellent flame-retarding properties can be imparted to thermoplastic polymers by incorporating into the polymer a synergistic combination of ammonium polyphosphate and a compound conforming to at least one of the following formulae (III) R! o crni cmomo N) wherein R R R R R and R are, individually, methyl ethyl or methoxy radicals, and R and R can combine to form a saturated, six-membered, hydrocarbon ring in conjunction with two adjacent carbon atoms of the benzene ring; a and b are, individually, whole integers of 0-2, inclusive; c and d are, individually, whole integers of 03, inclusive; e and f are, individually, whole integers of 04, inclusive; w is a whole integer of 2-6, inclusive; y is a whole integer of 2-4, inclusive, and z is a whole integer of 2-6, inclusive.
Among the preferred compounds are those represented by Formula I, including 5,8-bis[bis(2- cyanoethyl)phosphonyl-methylene]tetralin; l ,4- bis[bis(2-cyanoethyl)phosphonylmethylene]-2,3,5,6- tetramethyl benzene; l ,2,4,5-tetrakis[ bis-( 2- cyanoethyl)phosphonylmethylene]benzene; 2,4,6- tris[bis(Z-cyanoethyl)phosphonylmethylenelmesitylene; and l,4-phenylene-bis[bis(2-cyanoethyl)phosphonylmethylene; 2,4-bis[bis(2- cyanoethyl)phosphonylmethylene l ,3 ,S-trimethyl benzene and the like.
Compounds falling within the scope of Formulae II and III include l,5-bis[bis(2-cyanoethyl)phosphonylmethylene lnaphthalene; 9, l 0-bis[ bis( 2-cyanoethyl phosphonylmethylene]anthracene; 2,6-bis[bis(2- cyanoethyl)phosphonylmethylene]naphthalene; 2,3,6- tris[bis(2-cyanoethyl)phosphonylmethylene]naphthalene; 2,3,6-tris[bis(2- cyanoethyl)phosphonylmethylene]anthracene; 2,6,9,- l0-tetra[bis(2-cyanoethyl)phosphonylmethylene]anthracene; 1,6-bis[bis(2- cyanoethyl)phosphonylmethylene]-2-methoxy naphthalene; 2,3-bis[bis(2- cyanoethyl)phosphonylmethylene]-6,7- diethylanthracene and the like.
The poly (phosphine oxide) compounds used in forming the novel flame-retardant combinations of the instant invention are readily prepared by reacting bis(2-cyanoethyl)phosphine oxide with the appropriately substituted aromatic compound, in accordance with the general reaction:
wherein X is a halogen and x, n, m, R, R and AR are as set forth above.
The intermediate halomethylated aromatic compounds may conveniently be prepared by reacting the corresponding benzene, naphthalene or anthracene ages.
with formaldehyde and a hydrogen halide e.g., hydrogen chloride; hydrogen bromide etc., according to known procedures such as those disclosed in US. Pat. Nos. 2,945,894; 2,951,100; 2,973,391; 3,069,480. Alternatively, chlorination of the alkyl group or groups of the appropriate methyl benzene, methyl naphthalene or methyl anthracene in the presence of suitable catalysts, see US. Pat. No. 2,926,202, or with chlorine absorbed on zeolite and under reactive conditions, see US. Pat. No. 2,956,084, may be effected.
The poly (phosphine oxides) may be prepared according to the above general reaction in an organic solvent which is inert to the reaction and the components thereof. Methanol has been found to be an effective solvent, however, other alcohols may also be used. The reaction is best conducted in the presence of a proton acceptor such as a strong base e. g. potassium or sodium hydroxide, in amounts equivalent to the amount of hydrogen halide evolved.
The reaction is generally conducted at a temperature ranging from about 10C. to about 60C. under atmospheric pressure. Subatmospheric or superatmospheric pressure can be used, if desired. No catalysts are necessary.
The ammonium polyphosphates which constitute the second critical component of my novel flame-retardant compositions are well known in the art as shown in U.S. Pat. Nos. 3,423,343 and 3,513,114, which patents are hereby incorporated herein by reference. These ammonium polyphosphates are generally substantially waterinsoluble and possess a plurality of P-O-P type link- They can be represented by formula wherein g is an integer having an average value greater than 10, h/g is between about 0.7 and about 1.1 and the maximum value of h is equal to g+2. They are straight or branched chain structures having nearly all the nitrogen present therein as ammonical nitrogen. The average numerical value of g, using end group titration after acid formation, is from about 20-400, while using the light scattering method, the average weight value of n is above about 500, preferably 500l00,000 and especially preferably LOGO-30,000. The ammonium polyphosphates exhibit different crystalline forms but are also found in the non-crystalline or amorphous form also.
The combination of poly (phosphine oxide) and ammonium polyphosphate may be incorporated into the thermoplastic polymers in flame-retarding amounts. Concentrations of from about l25 percent, by weight, preferably from about 15-25 percent, by weight, based on the weight of the polymer, of the combination have been found effective. The ratio of poly (phosphine oxide) to ammonium polyphosphate should range from about 2:1 to about 1:2, respectively.
The novel compositions of my invention may be incorporated into the polymers by any known method. For example, the composition may be combined with the polymer by milling the two on a two-roll mill, mixing in a Banbury mixer, extrusion, injection molding or the like. The combination may also be incorporated into the polymer by adding it to the polymerization media during the polymer manufacture, provided the ingredients, catalysts etc. therein are inert thereto.
The thermoplastic polymers to which the novel poly (phosphine oxide)-ammonium polyphosphate compositions may be incorporated to produce the novel flame-retarded compositions of the instant invention are generally those produced from at least one ethylenically unsaturated monomer, wherein the monomer, or monomers, are polymerized, by any known method, via the ethylenic unsaturation therein. Preferred examples of polymers conforming to this definition include the polyolefins i.e., those polymers produced from ethylene, propylene etc. including copolymers thereof with such monomers as vinyl acetate etc. and homopolymers thereof i.e., polyethylene; polypropylene etc. I may also use the linear aromatic polyesters such as polyethylene terephthalate; polybutylene terephthalate; poly (l,4-cyclohexanedimethylene )terephthalate etc.; the polyalkylene oxides such as polyethylene oxide; nylon; rayon; polyphenylene oxide; butadiene polymers such as the so-called impact polymers i.e., acrylonitrilebutadiene-styrene polymers; acrylonitrilestyrene-methyl methacrylate grafted polybutadiene; cellulose acetate and propionate; etc. Further examples of polymers which may be flameproofed are set forth in US. Pat. No. 3,284,543, hereby incorporated herein by reference.
It is within the scope of the present invention to incorporate such ingredients as plasticizers, dyes, pigments, fillers, stabilizers, antioxidants, antistatic agents etc. into my novel flame-retarded compositions without detracting from the advantageous properties exhibited thereby.
The following examples are set forth for purposes of illustration only and are not to be construed as limitations on the present invention except as set forth in the appended claims. All parts and percentages are by weight unless otherwise specified.
EXAMPLE 1 Ten parts of l,4-bis[bis(2-cyanoethyl)phosphonyl methylene]2,3,5,6-tetramethyl benzene and 15 parts of ammonium polyphosphate are dry blended with polypropylene, extruded at 420F. and chopped into pellets. The pellets are then injection molded at 400-450F. in bars /4 inch X Va inch X 5 inches. Sample bars are then measured for flammability in accordance with Underwriters Laboratory Test UL-94 be fore and after subjection to UL Water Extraction Test, Subject 746, Mar. 1, 1957, paragraph E6. The water extraction test requires that the samples be immersed in water at C. for 7 days, the water being changed daily for the first five days. At the end of the immersion, the bars are dried in a dessicator before burning. Before and after extraction, each bar is designated as self-extinguishing.
EXAMPLE 2 When the concentration of the ammonium polyphosphate of Example 1 is reduced to 10 parts, all else remaining equal, the designation of the bars, before and after extraction, is again self-extinguishing.
Following the procedure of Example 1, various other poly (phosphine oxides) are substituted for that disclosed therein, blended with ammonium phosphate, incorporated into a thermoplastic polymer in the amounts indicated and tested using Test UL-94. The results are set forth in Table 1, below.
Table 1 Test Results Before After Ex. Poly (Phosphrne Ox1de)-% Polyphosphate-% Polymer Extraction Extraction 3 1,2,4,5-tetrakis[bis(Zcyanoethyl) Polypropylene SE SE phosphonylmethylene]benzene-8% 4 2,4,6-tris[bis(2-cyanoethyl) 10% Polyethylene SE SE phosphonylmethylene]mesitylene-10% 5 l,4-phenylcnebislbis(2-cyanoethyl) Polypropylene SE SE phosphonylmethylene]-l0% 6 4,6-bis[ bis( Z-cyanoethyl )phosphonyl- 8% Poly(1.4-cyelo SE SE methylcncll ,3dimcthyl benzene-12% hexanedimethylene) Terephthalate 7 2,5 bislbis(2-cyanoethyl)phosphonyl- 9% Polybutylene SE SE methylene 1- l ,4-dimethoxybenzene- 1 0% Terephthalate 8 Hexa[bis(2-cyanoethyl)phosphonyll0% Polypropylene SE SE methylene]benzene-8% 9 l,2,4.5,6'penta[bis(2-cyanoethyl) 10% Polyethylene SE SE phosphonylmethylene benzene-8% l0 l,4-bis[bis(2 cyanoethyl)phosphonyl- 10% Polyethylene SE SE methylene ]-2,S-diethylbenzenel 0% ll 1,5-bis[bis(2-cyanoethyl) phosphonyl 10.0% Polypropylene SE SE methylenelnaphthalene-10.0%
l2 9,10-bis[bis(2-cyanoethyl)phosphonyl- 10.0% Polypropylene SE SE methylene lanthracenel 0.0%
13 5,8-bis[bis( 2-cyanoethyl )phosphonyl- 10.0% Polypropylene SE SE methylene ltetralin- 1 0.0%
14 2,4-bis[bis(2-cyanoethyl)phosphonyl- 10.0% Polyethylene SE SE methylenel-l,3,5-trimethyl benzene-10.0%
SE=Self-extinguishing In addition to the superior results exhibited above by the synergistic combination of the ammonium polyphosphate and poly (phosphine oxide), I have also discovered that these unique combinations can be further modified by the incorporation therewith, into thermoplastic polymers, of various metal oxides and/or carbonates. The addition of these oxides and carbonates results in the production of polymers which are not only rendered flame-retardant but non-dripping, i.e. when the polymer is burned, the material does not drip, either as a burning or a molten mass.
The metal oxides or carbonates are added to the polymer in an amount ranging from about 0.5 percent to about 5 percent, by weight, based on the weight of the polymer. The manner in which the metal oxide or carbonate is added is not critical and it can be added to the polymer before, along with or after the phosphine oxide-ammonium polyphosphate combination. Arnourrtshigher than about 5 percent are generally undesirable. l have found that alkaline earth metal oxides such as barium oxide, magnesium oxide, etc.; alkaline earth metal carbonates such as magnesium carbonate, calcium carbonate etc.; Group IV-A metal oxides such as silicon dioxide, stannic oxide, etc.; titanium dioxide; zinc oxide; antimony oxide and the like can be used. While some of the compounds function at low concentrations, e.g., about 0.5 percent but not at about 5.0 percent, others perform at the higher level only. In all cases, however, the metal oxides or carbonates function to prevent dripping in a synergistic manner with the flame-retardant combination at a concentration With n he a v ra g The examples below clearly illustrate the unique effect afforded by the use of the oxide or carbonate in conjunction with the flame-retardant combinations of the examples above. The tests used, percentages, manner of incorporation, et conform to those enumerated aboye. Therwi s forth .iptTab s L.
Table II Poly (Phosphine Oxide)-ammonium Polyphosphate Flame Table II Continued Poly (Phosphine Oxide)-ammonium Polyphosphate Flame =Melt lndex Method of preparing specimen used. In this method the polymer and flame-retardant are EXAMPLE 28* When the flame-retardant composition of Example 6 of Table I is utilized to flame-proof polypropylene at a ratio of poly (phosphine oxide)-ammonium polyphosphate-titanium dioxide of /1, the flammability is rated self-extinguishing.
* See Table I1 footnote EXAMPLE 29* The procedure of Example 21 is again conducted except that a ratio of poly (phosphine oxide) to ammonium polyphosphate to titanium dioxide is 10/10/1 is used. The resultant composition is again rated as selfextinguishing.
* See Table ll footnote EXAMPLE 30* The procedure of Example 1 is again followed except that 2,5-bis[bis(2-cyanoethyl)phosphonylmethylene]- 1,4-dimethylbenzene is used at a ratio of poly (phosphine oxide) to ammonium polyphosphate to titanium dioxide of 10/ 10/ 1 is used and the polymer to which it is added is polypropylene. The resultant composition is again rated self-extinguishing.
* See Table [I footnote I claim:
1. A flame-retardant composition comprising (a) a compound having the formula wherein R and R are, individually, methyl, ethyl or methoxy radicals, AR is benzene, naphthalene, or anthracene and when AR is benzene, n and m are, individually, whole integers of 0-2, inclusive, x is a whole integer of 2-6, inclusive, and R and R can combine to form a saturated, six-membered, hydrocarbon ring in conjunction with two adjacent carbon atoms of the benzene ring, when AR is naphthalene, n and m are, individually, whole integers of O3, inclusive, and x is a whole integer of 2-4, inclusive, and when AR is anthracene, n and m are, individually, whole integers of 0-4, inclusive, and x is a whole integer of 2-6, inclusive, and (b) ammonium polyphosphate.
dry blended and extruded into an irregular shaped extrudate. This extrudale is then tested.
2. A composition according to claim 1 wherein AR is benzene, R and R are methyl, and x, n and m are 2.
3. A composition according to claim 1 wherein AR is benzene, x is 4 and n and m are 0.
4. A composition according to claim 1 wherein AR is benzene, R and R are methyl, x is 3, n is 2 and m is l.
5. A composition according to claim 1 wherein AR is benzene, R is methyl, x is 2, n is 2 and m is 0.
6. A composition according to claim 1 containing, in addition thereto, (c) from about 0.5 percent to about 5.0 percent, by weight, based on the weight of the polymer to which the composition is to be added of (1) an alkaline earth metal carbonate, (2) an alkaline earth metal oxide, (3) a Group IV-A metal oxide, (4) titanium dioxide, (5) zinc oxide or (6) antimony oxide.
7. A composition according to claim 6 wherein (c) is titanium dioxide.
8. A composition according to claim 6 wherein AR is benzene, R and R are methyl, and x, n and m are 2.
9. A composition according to claim 6 wherein AR is benzene, R and R are methyl, x, n and m are 2 and (c) is titanium dioxide.
10. A composition according to claim 9 wherein (a) is present at about 10 percent, (b) is present at about 10 percent and (c) is present at about 1.0 percent.
11. A composition according to claim 6 wherein AR is benzene, R is methyl, x is 2, n is 2, m is 0 and (c) is titanium dioxide.
12. A flame-retarded polymer comprising a polyolefin or a linear aromatic polyester and a flame-retarding amount of a composition of claim 1.
13. A flame-retarded composition according to claim 12 wherein AR is benzene, R and R are methyl and x, n and m are 2.
14. A flame-retarded composition comprising a polyolefin or a linear aromatic polyester and a flameretarding amount of a composition of claim 6.
15. A composition according to claim 14 wherein AR is benzene, R and R are methyl, and x, n and m are 2.
16. A composition according to claim 15 wherein (c) is titanium dioxide.
Claims (15)
- 2. A composition according to claim 1 wherein AR is benzene, R and R1 are methyl, and x, n and m are 2.
- 3. A composition according to claim 1 wherein AR is benzene, x is 4 and n and m are 0.
- 4. A composition according to claim 1 wherein AR is benzene, R and R1 are methyl, x is 3, n is 2 and m is 1.
- 5. A composition according to claim 1 wherein AR is benzene, R is methyl, x is 2, n is 2 and m is 0.
- 6. A composition according to claim 1 containing, in addition thereto, (c) from about 0.5 percent to about 5.0 percent, by weight, based on the weight of the polymer to which the composition is to be added of (1) an alkaline earth metal carbonate, (2) an alkaline earth metal oxide, (3) a Group IV-A metal oxide, (4) titanium dioxide, (5) zinc oxide or (6) antimony oxide.
- 7. A composition according to claim 6 wherein (c) is titanium dioxide.
- 8. A composition according to claim 6 wherein AR is benzene, R and R1 are methyl, and x, n and m are 2.
- 9. A composition according to claim 6 wherein AR is benzene, R and R1 are methyl, x, n and m are 2 and (c) is titanium dioxide.
- 10. A composition according to claim 9 wherein (a) is present at about 10 percent, (b) is present at about 10 percent and (c) is present at about 1.0 percent.
- 11. A composition according to claim 6 wherein AR is benzene, R is methyl, x is 2, n is 2, m is 0 and (c) is titanium dioxide.
- 12. A flame-retarded polymer comprising a polyolefin or a linear aromatic polyester and a flame-retarding amount of a composition of claim 1.
- 13. A flame-retarded composition according to claim 12 wherein AR is benzene, R and R1 are methyl and x, n and m are 2.
- 14. A flame-retarded composition comprising a polyolefin or a linear aromatic polyester and a flame-retarding amount of a composition of claim 6.
- 15. A composition according to claim 14 wherein AR is benzene, R and R1 are methyl, and x, n and m are 2.
- 16. A composition according to claim 15 wherein (c) is titanium dioxide.
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00374728A US3835119A (en) | 1973-06-28 | 1973-06-28 | Poly (phosphine oxide derivative) with ammonium polyphosphate as a flame retardant composition for polymers |
AR25422774A AR205889A1 (en) | 1973-06-28 | 1974-01-01 | NEW DERIVATIVES OF (BIS (2-CYANOETHYL) PHOSPHONYL METHYLENE) SAND FLAME RETARDERS AND THE COMPOSITION OF THEM |
AU69647/74A AU489910B2 (en) | 1973-06-28 | 1974-05-31 | Poly(phosphine oxide) flame-retardants |
GB2528974A GB1440536A (en) | 1973-06-28 | 1974-06-06 | Poly-phosphine oxide- flame-retardants |
CA202,115A CA1027582A (en) | 1973-06-28 | 1974-06-11 | Poly (phosphine oxide) flame-retardants |
DE19742429785 DE2429785A1 (en) | 1973-06-28 | 1974-06-21 | POLY (PHOSPHINOXYDE) AND COMPOSITIONS REFERRED TO IT |
FR7422334A FR2235132B1 (en) | 1973-06-28 | 1974-06-26 | |
BR527074A BR7405270D0 (en) | 1973-06-28 | 1974-06-27 | FLAME RETARDANT COMPOSITION |
IT5177774A IT1016212B (en) | 1973-06-28 | 1974-06-27 | POLY PHOSPHINE OXIDE USEFUL AS FIREPROOF AGENT AND COMPOSITION CONTAINING SAID COMPO STO |
CH886574A CH606061A5 (en) | 1973-06-28 | 1974-06-27 | |
NL7408786A NL7408786A (en) | 1973-06-28 | 1974-06-28 | |
ES427776A ES427776A1 (en) | 1973-06-28 | 1974-06-28 | Poly-phosphine oxide- flame-retardants |
JP7423374A JPS5054640A (en) | 1973-06-28 | 1974-06-28 |
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US00374728A US3835119A (en) | 1973-06-28 | 1973-06-28 | Poly (phosphine oxide derivative) with ammonium polyphosphate as a flame retardant composition for polymers |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0985706A1 (en) * | 1998-03-25 | 2000-03-15 | Teijin Limited | Resin composition |
WO2016033520A1 (en) * | 2014-08-29 | 2016-03-03 | The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas | Fire retardant materials and devices including same |
US10240090B2 (en) | 2014-08-29 | 2019-03-26 | The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas | Fire retardant materials and devices including same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2666078A (en) * | 1952-05-16 | 1954-01-12 | Arvey Corp | Bis-trichloroethyl benzene phosphonate |
US3663502A (en) * | 1970-10-29 | 1972-05-16 | American Cyanamid Co | Tertiary phosphine oxide-ammonium polyphosphate combinations as flame-retardants for propylene polymers |
US3783146A (en) * | 1972-04-03 | 1974-01-01 | American Cyanamid Co | Ammonium polyphosphate-phosphonium bromide-alkoxyalkanolamine as flame-retardants for polyolefins |
-
1973
- 1973-06-28 US US00374728A patent/US3835119A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2666078A (en) * | 1952-05-16 | 1954-01-12 | Arvey Corp | Bis-trichloroethyl benzene phosphonate |
US3663502A (en) * | 1970-10-29 | 1972-05-16 | American Cyanamid Co | Tertiary phosphine oxide-ammonium polyphosphate combinations as flame-retardants for propylene polymers |
US3783146A (en) * | 1972-04-03 | 1974-01-01 | American Cyanamid Co | Ammonium polyphosphate-phosphonium bromide-alkoxyalkanolamine as flame-retardants for polyolefins |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0985706A1 (en) * | 1998-03-25 | 2000-03-15 | Teijin Limited | Resin composition |
EP0985706A4 (en) * | 1998-03-25 | 2002-02-13 | Teijin Ltd | Resin composition |
WO2016033520A1 (en) * | 2014-08-29 | 2016-03-03 | The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas | Fire retardant materials and devices including same |
US10240090B2 (en) | 2014-08-29 | 2019-03-26 | The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas | Fire retardant materials and devices including same |
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